Meta-thiocarbamyl phenylene amides and ureas and their utility as herbicides

ABSTRACT

Meta-thiocarbamyl phenylene amides and ureas having the formula   IN WHICH R&#39;&#39; is alkyl or benzyl and R is alkyl, monoalkylamino, N,N-di-substituted amino wherein said substituents are independently selected from the group consisting of alkyl, alkoxy, furfuryl and cycloalkenyl. The compounds of this invention are useful as herbicides.

ite States Patent [1 1 Teach et al.

META-THIOCARBAMYL PI-IENYLENE AMIDES AND UREAS AND THEIRv UTILITY ASHERBICIDES Inventors: Eugene G. Teach, El Cerrito; Duane R. Arneklev,Sunnyvale, both of Calif.

Stauffer Chemical Company, New York,N.Y.

Filed: Nov. 2, 1970 Appl. No.: 86,379

Assignee:

US. Cl. ..260/347.2, 260/455 A, 260/453 R,

71/88, 7l/l00 Int. Cl ..C07d 5/16, C070 153/07 Field of Search ..260/455A, 347.2

References Cited OTHER PUBLICATIONS Browne et al., Chem. Abstr., Vol. 28(1934) 26891.

[ 1 Mar. 27, 1973 Primary Examiner-Alex Maze] Assistant ExaminerBernardDentz Attorney-Daniel C. Block, Edwin II. Baker, Albert J. Adamcik andHarry A. Pacini [57] ABSTRACT Meta-thiocarbamyl phenylene amides andureas having the formula 30 Claims, N0 Drawings META-THIOCARBAMYLPHENYLENE AMIDES AND UREAS AND THEIR UTILITY AS HERBICIDES Thisinvention relates to certain novel substituted meta-thiocarbamylphenylene amides and ureas which are useful as herbicides. The compoundsof the present invention are new compositions of matter and correspondto the general formula ii my-c-s-n in which R is alkyl or benzyl and Ris alkyl, monoalkylamino, N,N-di-substituted amino wherein saidsubstituents are independently selected from the group consisting ofalkyl, alkoxy, furfuryl and cycloalkenyl.

In the above description, the following preferred embodiments areintended for. the various substituent groups: for R, alkyl preferablyincludes, unless otherwise provided for, those members which containfrom one to 10 carbon atoms, inclusive, in both straight chain andbranched chain configurations, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, amyl, isoamyl,2,4,4-trimethylpentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl,nonyl, and decyl; for R and when used as a substituent on amino in R,alkyl preferably includes those members which contain from one to sixcarbon atoms in straight and branched chain configurations, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, amyl, isoamyl,n-hexyl and isohexyl; the term cycloalkenyl, preferably includes thosemembers containing at least one olefinic double bond and containing fromthree to seven carbon atoms, inclusive, for example, cyclopropenyl,cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and the like;the term alkoxy, preferably includes those members of the group whichcontain from one to six carbon atoms, such as methoxy, ethoxy, propoxy,and hexoxy and their isomers in branch chained configurations.

The compounds of this invention have been found to be active herbicidesof a general type. That is, certain members of the class have been foundto be herbicidally effective against a wide range of plant species. Amethod of controlling undesirable vegetation of the present inventioncomprises applying an herbicidally effective amount of theabove-described compounds to the area or plant locus where control isdesired.

An herbicide is used herein to mean a compound which controls ormodifies the growth of plants. By a growth controlling amount" is meantan amount of compound which causes a modifying effect upon the growth ofplants. Such modifying effects include all deviations from naturaldevelopment, for example, killing, retardation, defoliation,desiccation, regulation, stunting, tillering, stimulation, dwarfing andthe like. By plants" it is meant germinant seeds, emerging seedlings,and established vegetation, including the roots and above-groundportions.

The compounds of the present invention are prepared by severaldifferentmethods, depending upon the nature of the starting materials and theproducts desired. For example, the ineta-thiocarbamyl phenylene ureasare prepared by reacting a suitable aminophenyl urea with a suitablesubstituted chlorothiolformate in the presence of a tertiary amine, suchas triethylamine. The reactions proceed readily in the liquid phase. Theemployment of a solvent is also useful, facilitating processing, as wellas agitation of the reactants. Solvents such as acetone are convenientlyemployed. The reactions are carried out at temperatures that permitoperation in the liquid phase. The temperatures are between about roomtemperature and reflux temperature of the solvent, if a solvent isemployed. When preparing meta-thiocarbamyl phenylene amides, a suitablemeta-amino anilide is reacted with a substituted chlorothiolformate inthe presence of a tertiary amine, such as, triethylamine. In eachinstance after the reaction is complete, the recovery of the product iscarried out by normal work-up procedures such as crystallization,sublimation or distillation.

The compounds of the present invention and their preparation are moreparticularly illustrated by the following examples. Following theexamples is a table of compounds which are prepared according to theprocedures described herein.

EXAMPLE 1 EXAMPLE [I Preparation of3-propionamidophenyl-S-t-butylthiolcarbamate Eleven and one-half gramsof 3-amino propionani- "lide is dissolved in ml. of acetone and 7.1 g.of

triethylamine added. Ten and eight-tenths grams of tbutylchlorothiolformate is added dropwise with stirring. At the conclusion ofthe reaction, the mixture is poured into approximately 500 ml. of coldwater and the product, which crystallized out, is filtered off andwashed with dilute NaOl-l, dilute HCl and water and dried under vacuum.There is obtained 17.2 g., mp. 17 l-l 73C., of the title compound.

EXAMPLE I Preparation of l(3-t-Butylthiocarbamylphenyl) 3- ethyl ureaTwelve and one-half grams of l(3'-amino phenyl) 3- ethyl urea isdissolved in 100 ml. of acetone and 7.1 g. of triethylamine added. Tenand seven-tenths grams of t-butyl chlorothiolformate is added dropwiseand when reaction is complete, the mixture is poured into approximately500 ml. of cold water. The solid product is washed in a blender withdilute NaOH, filtered and washed with dilute HCl and water and driedunder vacuum. Yield is 17.7 g., m.p. 158169C. The product is taken up inisopropyl alcohol and the insoluble fraction (2.3 g., m.p. 341343C.) isflltered off. The lPA solution is treated with water and the productrecovered by filtration. There is obtained 12.8 g., m.p. 153-155C., withdecomposition, of the title compound.

EXAMPLE IV Preparation of 1(3'-Isopropylthiocarbamylphenyl) 3- methylurea Eleven and one-half grams of l(3-amino phenyl)3- methyl urea isdissolved in 100 ml. of acetone and 7.1 g. of triethylamine added.Isopropyl chlorothiolformate, 9.7 g., is added dropwise with stirringand when reaction is complete, the mixture is poured into approximately500 ml. of cold water. The product is recovered by filtration and washedwith dilute NaOl-l, dilute HCl, water and dried in the vacuum oven.There is obtained 16 g., m.p. 175-178C., of the title compound.

EXAMPLE V Preparation of 1(3'-Buty1thiocarbamylphenyl)3,3- dimethyl ureaTen and eight-tenths grams of 1(3'-amino phenyl) 3,3-dimethyl urea isdissolved in 100 ml. of acetone and 7.1 g. of triethylamine is added.Nine and two-tenths grams of t-butylchlorothiolformate is added dropwisewith stirring. When reaction is complete, the mixture is poured intowater and a viscious oil precipitated. The product is taken up inmethylene dichloride and washed with dilute HCl and dried over magnesiumsulfate. The methylene chloride is taken off under vacuum, leaving asolid foam. There is obtained 15.9 g., m.p. 68-7 1C., of the titlecompound.

The following is a table of the compounds which are prepared accordingto the aforementioned procedures. Compound numbers have been assigned tothem and are used for identification throughout the balance of thespecification.

HERBICIDAL SCREENING TESTS As previously mentioned, the herein describedcompounds produced in the above-described manner are phytotoxiccompounds which are useful and valuable in controlling various plantspecies. Compounds of this invention are tested as herbicides in thefollowing manner.

Pre-emergence herbicide test. On the day preceding treatment, seeds ofseven different weed species are planted in individual rows using onespecies per row across the width of the flat. The seeds used are hairycrabgrass (Digitaris sanguinalis (L.) Scop.), yellow foxtail (Setariaglauca (L.) Beauv.), watergrass (Echinochloa crusgalli (L.) Beauv.),California red oat (Avena sativa (L.)), redroot pigweed (Amaranthusretroflexus (L.)), Indian mustard (Brassica juncea (L.) Coss.) and curlydock (Rumex crispus (L.)). Ample seeds are planted to give about 20 to50 seedlings per row, after emergence, depending on the size of theplants. The flats are watered after planting. The spraying solution isprepared by dissolving 50 mg. of the test compound in 3 ml. of asolvent, such as acetone, containing 1 percent Tween 20 (polyoxyethylenesorbitan monolaurate). The following day each flat is sprayed at therate of 20 pounds of the candidate compound per gallons of solution peracre. An atomizer is used to spray the solution onto the soil surface.The flats are placed in a greenhouse at 80 F. and watered regularly. Twoweeks later the degree of weed control is determined by comparing theamount of germination and growth of each weed in the treated flats withweeds in several untreated control flats. The rating system is asfollows:

0 no significant injury (approximately 0-10 per cent control) 3 slightinjury (approximately 10-40 per cent control) 6 moderate injury(approximately 40-70 per cent control) 9 severe injury or death(approximately 70-100 per cent control) An activity index is used torepresent the total activity on all seven weed species. The activityindex is the sum of the numbers divided by 3, so that an activity indexof 21 represents complete control of all seven weeds. The results ofthis test are reported in Table II.

Post-emergence herbicide test. Seeds of five weed species, includinghairy crabgrass, watergrass, California red oats, Indian mustard, and curly dock and one crop, pinto beans (Phaseolus vulgaris), are planted inflats as described above for pre-emergence screening. The flats areplaced in the greenhouse at 72-85F. and watered daily with a sprinkler.About 10 to 14 days after planting, when the primary leaves of the beanplant are almost fully expanded and the first trifoliate leaves are juststarting to form, the plants are sprayed. The spray is prepared byweighing out 50 mg. of the test compound, dissolving it in 5 ml. ofacetone containing 1 percent Tween 20 (polyoxyethylene sorbitanmonolaurate) and then adding 5 ml. of water. The solution is sprayed onthe foliage using an atomizer. The spray concentration is 0.5 percentand the rate would be approximately 20 lb/acre if all of the spray wereretained on the plant and the soil, but some spray is lost so it isestimated that the application rate is approximately 12.5 lb/acre.

Beans are used to detect defoliants and plant growth regulators. Thebeans are trimmed to two or three plants per flat by cutting off theexcess weaker plants several days before treatment. The treated plantsare placed back in the greenhouse and care is taken to avoid sprinklingthe treated foliage with water for three days after treatment. Water isapplied to the soil by means of a slow stream from a watering hosetaking care not to wet the foliage.

Injury rates are recorded 14 days after treatment. The rating system isthe, same as described above for the preemergence test where (3), (6),and (9) are used for the different rates of injury and control. Theinjury symptoms are also recorded. The maximum activity index forcomplete control of all the species in the post-emergence screening testis 18. This index represents the sum of the rating numbers obtained withthe six plant species used in the test divided by 3. The herbicideactivity index is shown in Table 11.

TABLE II I-IERBICIDAL ACTIVITY SCREENING RESULTS Herbicidal activityindex" Compound Pre-emergence Post-emergence number (20lb/A) (12.5 lb/A)l 9 l2 2 10 14 3 l2 l8 4 l2 l7 5 l0 l6 6 13 7 l2 l3 8 6 l2 9 6 l2 l0 412 ll 11 18 12 10 18 13 1 l2 14 21 l8 21 -100% control of all sevenplant species tested pre-emergence.

18 70-100% control of all six plant species tested post-emergence.

The compounds of the present invention are used as pre-emergence orpost-emergence herbicides and are applied in a variety of ways atvarious concentrations. In practice, the compounds are formulated withan inert carrier, utilizing methods well-known to those skilled in theart, thereby making them suitable for application as dusts, sprays, ordrenches and the like, in the form and manner required. The mixtures canbe dispersed in water with the aid of a wetting agent or they can beemployed in organic liquid compositions, oil and water, water in oilemulsions, with or without the addition of wetting, dispersing oremulsifying agents. An herbicidally effective amount depends upon thenature of the seeds or plants to be controlled and the rate ofapplication varies from 1 to approximately 50 pounds per acre.

The phytotoxic compositions of this invention employing an herbicidallyeffective amount of the compound described herein are applied to theplants in the conventional manner. Thus, the dust and liquidcompositions can be applied to the plant by the use of power-dusters,boom and hand sprayers and spraydusters. The compositions can also beapplied from airplanes as a dust or a spray because they are effectivein very low dosages. In order to modify or control growth of germinatingseeds or emerging seedlings, as a typical example, the dust and liquidcompositions are applied to the soil according to conventional methodsand are distributed in the soil to a depth of at least one-half inchbelow the soil surface. It is not necessary that the phytotoxiccompositions be admixed with the soil particles and these compositionscan be applied merely by spraying or sprinkling the surface of the soil.The phytotoxic compositions of this invention can also be applied byaddition to irrigation water supplied to the field to be treated. Thismethod of application permits the penetration of the compositions intothe soil as the water is absorbed therein. Dust compositions, granularcompositions or liquid formulations applied to the surface of the soilcan be distributed below the surface of the soil by conventional meanssuch as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain otheradditaments, for example, fertilizers, pesticides and the like, used asadjuvant or in combination with any of the above-described adjuvants.Other phytotoxic compounds useful in combination with theabove-described compounds include, for example, 2,4-dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid,2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amidesthereof; triazine derivatives, such as2,4-bis(3-methoxypropylamino)-6-methyl-thio- S-Triazine;2-chloro-4-ethylamino-6-is0propylamino- S-triazine, and2-ethylamino-4-isopropylamino-6- methylmercapto-S-triazine, ureaderivatives, such as 3- (3,4-dichlorophenyl)-l ,l-dimethyl urea and3-(pchloro-phenyl)-1,l-dimethyl urea and acetamides such asN,N-diallyl-a-chloroacetamide, N-(achloroacetyl)hexamethylene imine, andN,N-diethyl-abromacetamide, and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic; and thiocarbamates, such as S-propyldipropylthiocarbamate; S-ethyldipropylthiocarbamate,S-ethylcyclohexyl-ethylthiocarbamate; S-ethylhexahydro-ll-l-azepine-l-carbothioate and the like. Fertilizers usefulin combination with the active ingredients include, for example,ammonium nitrate, urea and superphosphate. Other useful additamentsinclude materials in which plant organisms take root and grow, such ascompost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constitutingan effective amount in the best mode of administration in the utilitydisclosed, is readily determinable by those skilled in the art.

Various changes and modifications are possible without departing fromthe spirit and scope of the invention described herein and will beapparent to those skilled in the art to which it pertains. It isaccordingly intended that the present invention shall only be limited bythe scope of the claims.

What is claimed is:

l. A compound having the formula in which R is alkyl containing from oneto six carbon atoms, inclusive, or benzyl and R is alkyl containing fromone to l carbon atoms, inclusive, mono-alkylamino, N,N-di-substitutedamino wherein said substituents are independently selected from thegroup consisting of alkyl containing from one to six carbon atoms,inclusive, alkoxy containing from one to six carbon atoms, inclusive,furfuryl and cycloalkenyl containing from three to seven carbon atoms,inclusive.

2. A compound according to claim 1 in which R is alkyl and R is alkyl.

3. A compound according to claim 2 in which R is ethyl, and R is ethyl.

4. A compound according to claim 2 in which R isopropyl and R is ethyl.

5. A compound according to claim 2 in which R isopropyl and R istert.-butyl.

6. A compound according to claim 2 in which R isopropyl and R is1,1-dimethylbutyl.

7. A compound according to claim 2 in which R tert.-butyl and R isethyl.

8. A compound according to claim 2 in which R tert.-butyl and R istert.-butyl.

9. A compound according to claim 2 in which R is tert.-butyl and R is1,1-dimethylbutyl.

10. A compound according to claim 1 in which R is benzyl and R is alkyl.

11. A compound according to claim 10in which R is ethyl.

12. A compound according to claim 10in which R is tert.-butyl.

13. A compound according to claim 10 in which R is l,l-dimethylbutyl.

14. A compound according to claim 1 in which R is alkyl and R ismono-alkylamino.

15. A compound according to claim 14 in which R is isopropyl and R isethylamino.

16. A compound according to claim 14 in which R is tert.-butyl and R isethylamino.

17. A compound according to claim 14 in which R is isopropyl and R ismethylamino.

18. A compound according to claim 14 in which R is tert.-butyl and R ismethylamino.

19. A compound according to claim 1 in which R is benzyl and R ismono-alkylamino.

20. A compound according to claim 19 in which R is ethylamino.

21. A compound according to claim 19 in which R is methylamino.

22. A-compound according to claim 1 in which R is alkyl and R isdialkylamino.

23. A compound according to claim 22 in which R is methyl and R isN-methyl-N-n-butylamino.

24. A compound according to claim 22 in which R is tert.-butyl and R isN-methyl-N-n-butylamino.

25. A compound according to claim 1 in which R is alkyl and R isN-alkyl-N-alkoxyamino.

26. A compound according to claim 25 in which R is methyl and R isN-methyl-N-methoxyamino.

27. A compound according to claim 25 in which R is isopropyl and R isN-methyl-N-methoxyamino.

28. A compound according to claim 25 in which R is tert.-butyl and R isN-methyl-N-methoxyamino.

29. A compound according to claim 1 in which R is alkyl and R isN-alkyl-N-furfurylamino.

30. A compound according to claim 1 in which R is alkyl and R isN-alkyl-N-cycloalkenylamino.

s r-ra e

2. A compound according to claim 1 in which R'' is alkyl and R is alkyl.3. A compound according to claim 2 in which R'' is ethyl, and R isethyl.
 4. A compound according to claim 2 in which R'' is isopropyl andR is ethyl.
 5. A compound according to claim 2 in which R'' is isopropyland R is tert.-butyl.
 6. A compound according to claim 2 in which R'' isisopropyl and R is 1,1-dimethylbutyl.
 7. A compound according to claim 2in which R'' is tert.-butyl and R is ethyl.
 8. A compound according toclaim 2 in which R'' is tert.-butyl and R is tert.-butyl.
 9. A compoundaccording to claim 2 in which R'' is tert.-butyl and R is1,1-dimethylbutyl.
 10. A compound according to claim 1 in which R'' isbenzyl and R is alkyl.
 11. A compound according to claim 10 in which Ris ethyl.
 12. A compound according to claim 10 in which R istert.-butyl.
 13. A compound according to claim 10 in which R is1,1-dimethylbutyl.
 14. A compound according to claim 1 in which R'' isalkyl and R is mono-alkylamino.
 15. A compound according to claim 14 inwhich R'' is isopropyl and R is ethylamino.
 16. A compound according toclaim 14 in which R'' is tert.-butyl and R is ethylamino.
 17. A compoundaccording to claim 14 in which R'' is isopropyl and R is methylamino.18. A compoUnd according to claim 14 in which R'' is tert.-butyl and Ris methylamino.
 19. A compound according to claim 1 in which R'' isbenzyl and R is mono-alkylamino.
 20. A compound according to claim 19 inwhich R is ethylamino.
 21. A compound according to claim 19 in which Ris methylamino.
 22. A compound according to claim 1 in which R'' isalkyl and R is dialkylamino.
 23. A compound according to claim 22 inwhich R'' is methyl and R is N-methyl-N-n-butylamino.
 24. A compoundaccording to claim 22 in which R'' is tert.-butyl and R isN-methyl-N-n-butylamino.
 25. A compound according to claim 1 in whichR'' is alkyl and R is N-alkyl-N-alkoxyamino.
 26. A compound according toclaim 25 in which R'' is methyl and R is N-methyl-N-methoxyamino.
 27. Acompound according to claim 25 in which R'' is isopropyl and R isN-methyl-N-methoxyamino.
 28. A compound according to claim 25 in whichR'' is tert.-butyl and R is N-methyl-N-methoxyamino.
 29. A compoundaccording to claim 1 in which R'' is alkyl and R isN-alkyl-N-furfurylamino.
 30. A compound according to claim 1 in whichR'' is alkyl and R is N-alkyl-N-cycloalkenylamino.